Electrochemical lithium insertion into anatase-type TiO2:: An in situ Raman microscopy investigation

被引:120
作者
Hardwick, Laurence J. [1 ]
Holzapfel, Michael
Novak, Petr
Dupont, Loic
Baudrin, Emmanuel
机构
[1] Paul Scherrer Inst, Electrochem Lab, CH-5232 Villigen, Switzerland
[2] Univ Picardie, CNRS, UMR 6007, Lab React & Chim Solides, F-80039 Amiens, France
关键词
anatase TiO2; in situ Raman microscopy; electrochemical lithium insertion; nano-crystallites; optical skin depth;
D O I
10.1016/j.electacta.2007.02.050
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
Anatase type TiO2 has been previously largely reported as a candidate negative electrode material for lithium-ion batteries. We report here for the first time the complete in situ Raman study of lithium insertion and de-insertion into three variously nano-sized TiO2 anatase powders (Prolabo, ca. 80 nm. AK1, ca. 15 nm and MTi5 ca. 8 nm), of which AK1 and MTi5 show superior capacity and cyclability. From these measurements realized in a galvanostatic mode between 3 and 1 V versus Li/Li+, the phase transition from a tetragonal to an orthorhombic structure was clearly observed to take place at different quantities of x in LixTiO2. These results confirm the extension of the solid solution domain as particle size is reduced. For the smaller TiO2 nano-sized materials (AK1 and MTi5), a more pronounced decrease in band intensity when x > 0.3 for LixTiO2, was observed and may be related to the decrease in the optical skin depth linked to the conductivity increase as lithiation proceeds. (c) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:5357 / 5367
页数:11
相关论文
共 51 条
  • [41] In situ X-ray diffraction of lithium intercalation in nanostructured and thin film anatase TiO2
    van de Krol, R
    Goossens, A
    Meulenkamp, EA
    [J]. JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1999, 146 (09) : 3150 - 3154
  • [42] The life and times of lithium in anatase TiO2
    Wagemaker, M
    van Well, AA
    Kearley, GJ
    Mulder, FM
    [J]. SOLID STATE IONICS, 2004, 175 (1-4) : 191 - 193
  • [43] Nano-morphology of lithiated thin film TiO2 anatase probed with in situ neutron reflectometry
    Wagemaker, M
    van de Krol, R
    van Well, AA
    [J]. PHYSICA B-CONDENSED MATTER, 2003, 336 (1-2) : 124 - 129
  • [44] Quasi-in-situ reflection mode XANES at the TiK-edge of lithium intercalated TiO2 rutile and anatase
    Wagemaker, M
    Lützenkirchen-Hecht, D
    Keil, P
    van Well, AA
    Frahm, R
    [J]. PHYSICA B-CONDENSED MATTER, 2003, 336 (1-2) : 118 - 123
  • [45] Multiple li positions inside oxygen octahedra in lithiated TiO2 anatase
    Wagemaker, M
    Kearley, GJ
    van Well, AA
    Mutka, H
    Mulder, FM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (03) : 840 - 848
  • [46] Equilibrium lithium transport between nanocrystalline phases in intercalated TiO2 anatase
    Wagemaker, M
    Kentgens, APM
    Mulder, FM
    [J]. NATURE, 2002, 418 (6896) : 397 - 399
  • [47] Two phase morphology limits lithium diffusion in TiO2 (anatase):: A 7Li MAS NMR study
    Wagemaker, M
    van de Krol, R
    Kentgens, APM
    van Well, AA
    Mulder, FM
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (46) : 11454 - 11461
  • [48] WAGEMAKER M, 2006, P IMLB M BIARR FRANC
  • [49] Winter M, 1998, ADV MATER, V10, P725, DOI 10.1002/(SICI)1521-4095(199807)10:10<725::AID-ADMA725>3.0.CO
  • [50] 2-Z